Association and Structure of Thermosensitive Comblike Block Copolymers in Aqueous Solutions

The structures and association properties of thermosensitive block copolymers of poly(methoxyoligo( ethylene glycol) norbornenyl esters) in D2O were investigated by small angle neutron scattering (SANS). Each block is a comblike polymer with a polynorbornene (PNB) backbone and oligo ethylene glycol (OEG) side chains (one side chain per NB repeat unit). The chemical formula of the block copolymer is (OEG3NB) 79- (OEG6.6NB) 67, where subscripts represent the degree of polymerization (DP) of OEG and NB in each block. The polymer concentration was fixed at 2.0 wt % and the structural changes were investigated over a temperature range between 25 and 68°C. It was found that at room temperature polymers associate to form micelles with a spherical core formed by the block (OEG3NB) 79 and corona formed by the block (OEG6.6NB) 67 and that the shape of the polymer in the corona could be described by the form factor of rigid cylinders. At elevated temperatures, the aggregation number increased and the micelles became more compact. At temperatures around the cloud point temperature (CPT) T ) 60 °C a correlation peak started to appear and became pronounced at 68 °C due to the formation of a partially ordered structure with a correlation length ∼349 Å.

Stability of Order in Solvent-Annealed Block Copolymer Thin Films

ABSTRACT: One way to produce high order in a block copolymer thin film is by solution casting a thin film and slowly evaporating the solvent in a sealed vessel. Such a solvent-annealing process is a versatile method to produce a highly ordered thin film of a block copolymer. However, the ordered structure of the film degrades over time when stored under ambient conditions. Remarkably, this aging process occurs in mesoscale thin films of polystyrene-polyisoprene triblock copolymer where the monolayer of vitrified 15 nm diameter polystyrene cylinders sink in a 20 nm thick film at 22 °C. The transformation is studied by atomic force microscopy (AFM). We describe the phenomena, characterize the aging process, and propose a semiquantitative model to explain the observations. The residual solvent effects are important but not the primary driving force for the aging process. The study may lead to effective avenue to improve order and make the morphology robust and possibly the solvent-annealing process more effective.

Growth and Characterization of Silicon Carbide Thin Films Using a Nontraditional Hollow Cathode Sputtering Technique

Silicon carbide (SiC) is considered a suitable candidate for high-power, high-frequency devices due to its wide bandgap, high breakdown field, and high electron mobility. It also has the unique ability to synthesize graphene on its surface by subliming Si during an annealing stage. The deposition of SiC is most often carried out using chemical vapor deposition (CVD) techniques, but little research has been explored with respect to the sputtering of SiC. Investigations of the thin film depositions of SiC from pulse sputtering a hollow cathode SiC target are presented. Although there are many different polytypes of SiC, techniques are discussed that were used to identify the film polytype on both 4H-SiC substrates and Si substrates. Results are presented about the ability to incorporate Ge into the growing SiC films for the purpose of creating a possible heterojunction device with pure SiC. Efforts to synthesize graphene on these films are introduced and reasons for the inability to create it are discussed. Analysis mainly includes crystallographic and morphological studies about the deposited films and their quality using x-ray diffraction (XRD), reflection high energy electron diffraction (RHEED), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), Auger electron spectroscopy (AES) and Raman spectroscopy. Optical and electrical properties are also discussed via ellipsometric modeling and resistivity measurements. The general interpretation of these analytical experiments indicates that the films are not single crystal. However, the majority of the films, which proved to be the 3C-SiC polytype, were grown in a highly ordered and highly textured manner on both (111) and (110) Si substrates.

Social cohesion among kin, gene flow without dispersal and the evolution of population genetic structure in the killer whale (Orcinus orca)

In social species, breeding system and gregarious behavior are key factors influencing the evolution of large-scale population genetic structure. The killer whale is a highly social apex predator showing genetic differentiation in sympatry between populations of foraging specialists (ecotypes), and low levels of genetic diversity overall. Our comparative assessments of kinship, parentage and dispersal reveal high levels of kinship within local populations and ongoing male-mediated gene flow among them, including among ecotypes that are maximally divergent within the mtDNA phylogeny. Dispersal from natal populations was rare, implying that gene flow occurs without dispersal, as a result of reproduction during temporary interactions. Discordance between nuclear and mitochondrial phylogenies was consistent with earlier studies suggesting a stochastic basis for the magnitude of mtDNA differentiation between matrilines. Taken together our results show how the killer whale breeding system, coupled with social, dispersal and foraging behaviour, contributes to the evolution of population genetic structure.